DE102005051238A1 - Physical, thermal or thermal and actinic radiation curable aqueous mixtures, process for their preparation and their use - Google Patents

Abstract

Aqueous mixtures curable physically, thermally or thermally and with actinic radiation, containing DOLLAR A (A) at least one saturated, unsaturated and / or ionically and / or nonionically stabilized polyurethane that is grafted with olefinically unsaturated compounds as a binder, DOLLAR A (B) at least a color and / or effect pigment and DOLLAR A (C) at least one phosphoric acid ester of the general formula I: DOLLAR A (R · 1 · ORO) ¶3¶P = O, DOLLAR A where the variables have the following meaning: DOLLAR AR Alkanediyl groups with 2 to 10 carbon atoms and DOLLAR AR · 1 · alkyl group with 2 to 10 carbon atoms; DOLLAR A process for their production and their use.

Description

Territory of invention

The The present invention relates to new, physical, thermal or thermally curable and with actinic radiation, aqueous mixtures. It also concerns the present invention provides a novel process for the preparation of physically, thermally or thermally and curable with actinic radiation, aqueous Mixtures. Furthermore, the present invention relates to the use the new, physical, thermal or thermal and with actinic Radiation curable, aqueous Mixtures and those produced by the new process, physically, thermally or thermally curable and with actinic radiation, aqueous Mixtures.

As is known Tris (2-butoxylethyl) phosphate (hereinafter referred to as "TBEP" for brevity) as a plasticizer for Synthetic rubbers used (see Rompp Online 2005, "plasticizers").

TBEP and tris (2-hexoxyethyl) phosphate (hereinafter referred to as "THEP" for brevity) are used as defoamers, dispersing aids, freeze-thaw stabilizers, leveling agents, and over-rapid-drying agents in acrylic-based latex paints -, polyvinyl acetate, vinyl acrylic, vinyl ethylene, styrene-butadiene copolymer and Polyvinylchloridacryl latex used (see German Offenlegungsschrift DE 1794245 ).

From the German patent DE 100 43 405 C1 is a thermally curable waterborne basecoat or solid-color topcoat comprising at least one saturated, unsaturated and / or grafted with olefinically unsaturated compounds, ionically and / or nonionically stabilized polyurethane as a binder, at least one color and / or effect pigment and at least one trioorganophosphate such as tributyl phosphate , The trioorganophosphates are used to adjust the water vapor permeability of the basecoats or solid-color topcoats prepared from the known waterborne basecoats or solid-color topcoats. Their cooking limit is at a dry film thickness of 27 to 28 microns. However, their needlestick limit, ie the dry film thickness up to which no pinholes occur, must be raised further.

Task of invention

Of the It is an object of the present invention to provide new, physical, thermally or thermally curable and with actinic radiation, aqueous To provide mixtures containing at least one saturated, unsaturated and / or with olefinically unsaturated Compounds grafted, ionic and / or nonionic stability of the polyurethane as a binder and at least one color and / or effect pigment contain,

The new, physical, thermal or thermal and with actinic Radiation curable, aqueous Mixtures should be easily reproducible in a simple manner, be stable on storage, transportable and shear stable. They should be process easily in a simple manner, in particular apply, leave and cured quickly can be.

she should be very good for producing new, color and / or effect, thermosetting or thermoplastic materials that are also suitable for high layer thicknesses free of material defects, in particular free from Cookers and pinpricks, are.

Especially They should be considered new coating materials, adhesives and sealants as well Precursors of molded parts and films, especially as new coating materials, for the production of new color and / or effect coatings, Adhesive layers and seals as well as molded parts and foils, especially of new color and / or effect coatings.

The resulting new, color and / or effect coatings, in particular the new primer coatings, anti-corrosion coatings, Surfacer coats, Antistonechip primers, functional finishes, basecoats and solid colors, should at a high cooker limit a have high pinhole limit.

there the new, color and / or effect coatings should be the excellent performance characteristics of the known Coatings continue to exhibit, if not exceed. In particular, they should be free of light-dark shades (clouds) and have an excellent overall appearance (appearance).

Inventive solution

• (A) mindestens ein gesättigtes, ungesättigtes und/oder mit olefinisch ungesättigten Verbindungen gepfropftes, ionisch und/oder nichtionisch stabilisiertes Polyurethan als Bindemittel,
• (B) mindestens ein farb- und/oder effektgebendes Pigment und
• (C) mindestens einen Phosphorsäureester der allgemeinen Formel I: (R¹ORO)₃P=O (I),worin die Variablen die vorliegende Bedeutung haben: R Alkandiyl-Gruppe mit 2 bis 10 Kohlenstoffatomen und R¹ Alkylgruppe mit 2 bis 10 Kohlenstoffatomen;

enthalten und die im Folgenden als »erfindungsgemäße Gemische« bezeichnet werden.Accordingly, the new, physical, thermally or thermally and with actinic radiation curable, aqueous mixtures found that

• (A) at least one, unsaturated and / or with olefinically unsaturated compounds grafted, ionically and / or non-ionically stabilized polyurethane as a binder,
• (B) at least one color and / or effect pigment and
• (C) at least one phosphoric acid ester of the general formula I: (R ¹ ORO) ₃ P = O (I), wherein the variables have the following meaning: R alkanediyl group having 2 to 10 carbon atoms and R ¹ alkyl group having 2 to 10 carbon atoms;

and which are hereinafter referred to as "mixtures according to the invention".

It was also the new process for the preparation of the mixtures according to the invention found in which the components (A), (B) and (C) in the presence of water mixed together and the resulting mixture homogenized and hereinafter referred to as "inventive method" becomes.

Not last was the new use of the mixtures according to the invention and the method according to the invention prepared mixtures according to the invention for the Production of new, color and / or effect, thermosetting and thermoplastic materials, hereinafter referred to as "inventive use" becomes.

Further Invention objects go out of the description.

Advantages of invention

in the In view of the prior art, it was surprising and for the expert unpredictable that the task of the present invention underlying, by the mixtures according to the invention, the inventive method and the use according to the invention solved could be.

Especially it was surprising that the mixtures of the invention easily reproducible in a simple manner, storable, were transportable and shear stable. They settled in a simple way process easily, especially apply, and were able to quickly hardened become.

she were excellent in the context of the use according to the invention for the production of new, color and / or effect, duroplastic or thermoplastic, in particular duroplastic, materials, even at high layer thicknesses free of material defects, especially free from digesters and pinpricks.

Especially they were suitable as coating materials according to the invention, adhesives and sealants and precursors of moldings and films, especially as coating materials according to the invention, for the production of new color and / or effect coatings, Adhesive layers and seals as well as molded parts and foils, especially of new color and / or effect coatings.

The resulting coatings according to the invention, in particular the primer coatings according to the invention, Anticorrosion paints surfacer paints, Rockfall protection primers, functional coatings, basecoats and Solid topcoats, had at a particularly high cooker limit a high pinprick limit.

there showed the coatings according to the invention the excellent performance characteristics of the known Coatings continued to and even surpassed it in many cases. In particular, they were free of light-dark shades (clouds) and showed an excellent overall appearance (appearance).

Full Description of the invention

The mixtures according to the invention are watery. This means that their constituents described below (A), (B) and (C) and optionally (D) dissolved in water and / or are dispersed.

The mixtures according to the invention can physically curable be.

In the context of the present invention, the term "physical curing" means the curing of a mixture, in particular a coating material, by film formation by release of solvent from the mixture, wherein the linkage within the resulting thermoplastic material, in particular the coating, via looping of the polymer molecules of the binder (to see the term see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, Binders, pages 73 and 74.) Or else the filming takes place via the coalescence of binder particles (see Rompp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening," pages 274 and 275).

The mixtures according to the invention can be thermal curable be.

The thermal curing can over the so-called self-crosslinking of components of the mixtures according to the invention respectively.

to Adjustment of this property contain the mixtures according to the invention complementary reactive functional groups that interact with the existing hydroxyl groups and / or of these different complementary ones reactive functional groups thermally initiated and maintained Reactions, and / or autoreactive functional groups, who can react with themselves.

The thermal curing but also about the so-called foreign crosslinking of constituents of the mixtures according to the invention respectively.

to Adjustment of this property contain the mixtures according to the invention at least two constituents, each one kind of complementary reactive contain functional groups that thermally initiated each other and sustained reactions.

The mixtures according to the invention can be thermal and curable with actinic radiation which is also called dual-cure curing referred to as.

Around curable with actinic radiation to be present, the mixtures according to the invention with actinic Radiation activatable bonds that are activated by the irradiation and with other activated bonds of their type polymerization reactions and / or crosslinking reactions that after radical and / or ionic mechanisms.

Under Actinic radiation is here and below electromagnetic Radiation, such as near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, in particular UV radiation, or corpuscular radiation, like electron radiation, beta radiation, alpha radiation, proton radiation or neutron radiation, in particular electron radiation.

Especially are the mixtures according to the invention thermally curable, the physical cure the thermal curing support can.

The constituent of the mixtures according to the invention which is essential to the invention is at least one, in particular one, phosphoric acid ester (C) of the general formula I: (R ¹ ORO) ₃ P = O (I), wherein the variables have the meaning:
R alkanediyl group having 2 to 10, preferably 2 to 7 and especially 2 to 4 carbon atoms and
R ¹ alkyl group having 2 to 10, preferably 2 to 7 and especially 2 to 6 carbon atoms.

The Alkanediyl group R may be linear or branched. Preferably is she linear?

The alkyl group R ¹ may be linear or branched. Preferably, it is linear.

Prefers alkanediyl group R is selected from the group consisting of ethylene, trimethylene, Tetramethylene, pentamethylene, hexamethylene, heptane-1,7-diyl, octane-1,8-diyl, Nonane 1,9-diyl and Decan-1,10-diyl, more preferably from ethylene, trimethylene and Tetramethylene, selected. In particular, the alkanediyl group R is ethylene.

The alkyl group R ¹ is preferably selected from the group consisting of ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, particularly preferably from ethyl, propyl , n-butyl, n-pentyl and n-hexyl. In particular, the alkyl group R ^{1 is} n-butyl.

All the phosphoric esters (C) are particularly preferably selected from the group consisting of tris (2-butoxyethyl) phosphate (TBEP) and tris (2-hexoxyethyl) phosphate (THEP) selected. Especially TBEP is used.

Of the Content of the mixtures according to the invention on phosphoric acid ester (C) can vary widely and therefore perfectly meet the requirements be adapted to the individual case. The mixtures according to the invention preferably contain the phosphoric acid ester (C) in an amount of 0.1 to 5 wt .-%, preferably 0.5 to 4 wt .-% and in particular 1 to 3 wt .-%, each based on the mixture according to the invention.

Of the second essential constituent of the mixtures according to the invention is at least a saturated, unsaturated and / or with olefinically unsaturated Compounds grafted, ionically and / or nonionically stabilized Polyurethane (A), which is used as a binder (see Rompp Online 2005, "Binders") becomes.

• – DE 199 14 896 A1 , Spalte 4, Zeile 23, bis Spalte 11, Zeile 5, i. V. m. Spalte 1, Zeilen 9 bis 56, und Spalte 19, Zeile 12, bis Spalte 20, Zeile 6,
• – DE 44 37 535 A1 Seite 2, Zeile 24, bis Seite 6, Zeilen 22, und Seite 7, Zeile 20, bis Seite 8, Zeile 49,
• – DE 100 43 405 C1 , Spalte 11, Zeile 24, bis Spalte 12, Zeile 11,
• – DE 100 04 494 A1 , Spalte 5, Zeile 16, bis Spalte 11, Zeile 50, i. V. m. Spalte 1, Zeilen 10 bis 24, und Spalte 18, Zeilen 15 bis 31, und
• – DE 40 09 858 A1 , Spalte 6, Zeile 17, bis Spalte 10, Zeile 23, und Spalte 16, Zeilen 10 bis 35,

im Detail beschrieben.
oder der internationalen Patentanmeldung

• – WO 92/15405, Seite 2, Zeile 35, bis Seite 3 Zeile 22, Seite 3, Zeile 33, bis Seite 10, Zeile 33, Seite 14, Zeile 13, bis Seite 15, Zeile 13.

Polyurethanes (A) are customary and known and are described, for example, in the German patent applications

• - DE 199 14 896 A1 , Column 4, line 23, to column 11, line 5, i. V. m. Column 1, lines 9 to 56, and column 19, line 12, to column 20, line 6,
• - DE 44 37 535 A1 Page 2, line 24, to page 6, lines 22, and page 7, line 20, to page 8, line 49,
• - DE 100 43 405 C1 , Column 11, line 24, to column 12, line 11,
• - DE 100 04 494 A1 , Column 5, line 16, to column 11, line 50, i. V. m. Column 1, lines 10 to 24, and column 18, lines 15 to 31, and
• - DE 40 09 858 A1 , Column 6, line 17, to column 10, line 23, and column 16, lines 10 to 35,

described in detail.
or the international patent application

• - WO 92/15405, page 2, line 35, to page 3, line 22, page 3, line 33, to page 10, line 33, page 14, line 13, to page 15, line 13.

Of the Content of the mixtures according to the invention on the polyurethanes (A) can vary very widely and therefore excellent be adapted to the needs of each case. Preferably the polyurethanes (A) are used in the amounts as described in the above listed Patent applications are described. The content is preferably at 10 to 80 wt .-%, particularly preferably 15 to 70 wt .-% and in particular From 20 to 60% by weight, based in each case on the film-forming solids of the mixture according to the invention.

Here and below is under »film-forming Solid state «the sum to understand the constituents of a mixture according to the invention, the thermoset and thermoplastic according to the invention prepared therefrom Building materials.

Of the third essential component of the mixtures according to the invention is at least a color and / or effect pigment (B).

The Number of different color and / or effect pigments (B), which in a mixture according to the invention may vary widely and is aimed in particular after the visual effects and / or hues that are set should.

• – DE 103 06 358 A1 , Seite 6, Absätze [0055] bis [0058], würden oder
• – DE 100 04 494 A1 , Spalte 11, Zeile 51, bis Spalte 12, Zeile 34,

bekannt.Examples of suitable color and / or effect pigments (B) are known from the German patent applications

• - DE 103 06 358 A1 , Page 6, paragraphs [0055] to [0058], would or
• - DE 100 04 494 A1 , Column 11, line 51, to column 12, line 34,

known.

Of the Content of the mixtures according to the invention of color and / or effect pigments (B) can vary very widely. It depends in particular on the intensity of the optical effects and shades that should be set.

Of the Professional can do the for a desired one optical effect and / or hue suitable pigments and their amounts where appropriate, with the aid of its general expertise easy to select for orienting colorimetric examinations.

The mixtures according to the invention can still contain at least one additive (D). Preferably Additives (D) used, as customary in the field of coating materials and are known. The additives (D) are preferably selected from the group consisting of binders other than the binders (A), Crosslinking agents, neutralizing agents, catalysts for crosslinking, Adhesion promoters, additives for improving the substrate wetting, Additives for improving surface smoothness, matting agents, light stabilizers, Polymerization inhibitors, corrosion inhibitors, biocides, flame retardants, Initiators for thermal crosslinking, photoinitiators, of the pigments (B) different, fluorescent, electrically conductive and / or magnetic shielding pigments and metal powders, organic and inorganic, transparent or opaque fillers and nanoparticles, organic dyes, rheology aids, Leveling agents, wetting agents, emulsifiers, defoamers and from the phosphoric acid esters (C) various organic solvents, selected.

• – DE 103 06 358 A1 , Seite 6, Absatz [0059], bis Seite 7, Absatz (0068],
• – DE 100 04 494 A1 , Spalte 3, Zeile 38, bis Spalte 5, Zeile 9, und Spalte 12, Zeile 35, bis Spalte 15, Zeile 1, und
• – DE 199 14 896 A1 , wird das der Spalte 11, Zeile 6, bis Spalte 13, Zeile 52, und Spalte 14, Zeile 16, bis, Zeile 63,

bekannt.Examples of suitable additives (D) are from the German patent applications

• - DE 103 06 358 A1 , Page 6, paragraph [0059], to page 7, paragraph (0068],
• - DE 100 04 494 A1 , Column 3, line 38, to column 5, line 9, and column 12, line 35, to column 15, line 1, and
• - DE 199 14 896 A1 , that of column 11, line 6, to column 13, line 52, and column 14, line 16, to, line 63,

known.

Of the Content of the mixtures according to the invention The additives (D) can vary widely, making it optimal can be adapted to the respective purpose. Preferably the additives (D) in the usual and known, effective Used quantities. These are the expert due to its general Expertise, where the information in the aforementioned German patent applications can serve as a guide.

The film-forming solid contained in the mixtures according to the invention can vary widely and therefore meet the requirements of the respective Ver can be perfectly adapted for the purpose of It is a very particular advantage of the mixtures according to the invention that they can have a high content of film-forming solids. Preferably, the film-forming solid is 10 to 60 wt .-%, preferably 15 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on a mixture according to the invention.

Preferably become the mixtures according to the invention according to the inventive method prepared by adding at least one binder (A), at least a color and / or effect pigment (B) and at least one phosphoric acid ester (C) mixed together in the presence of water and the resulting Homogenized mixture. At least one additive is preferred (D) added.

Prefers be the usual and known mixing methods and devices such as ultrasonic baths, stirred tanks, Agitator mills, extruders, Kneader, Ultraturrax, in-line dissolver, static mixers, micromixers, sprocket dispersers, pressure relief nozzles and / or Microfluidizer, if appropriate with the exclusion of actinic radiation, used.

The mixtures according to the invention serve in the context of the inventive use of the preparation the thermoset and thermoplastic, in particular thermosetting, materials.

in the Framework of the use according to the invention the mixtures according to the invention are preferably used as coating materials according to the invention, Adhesives and sealants and as precursors according to the invention of moldings and films, in particular coating materials, the Production of coatings according to the invention, Adhesive layers and seals as well as molded parts and films, in particular Coatings.

Especially the coating materials of the invention are preferred as Primers, anti-corrosion coatings, functional coatings, fillers or primers, waterborne basecoats and solid-color topcoats, in particular aqueous basecoats, for the production Primer coatings, anti-corrosion coatings, functional coatings, Surfacer coatings, antistonechip primers, Basecoats and solid-color topcoats used.

Under Functional coatings are to be understood as coatings which are used in the Are able to take over several functions, such as the functions of a primer coat and a base coat.

The coatings according to the invention can be single-layered or multi-layered. Very particularly preferred are they are multilayered and can at least two coatings, in particular at least one Electrocoating, at least one primer coat or antistonechip primer and at least one basecoat and at least one clearcoat or at least one solid-color finish. Especially preferred include the multicoat paint systems according to the invention at least one basecoat and at least one clearcoat.

From It is particularly advantageous to use the basecoat of the multicoat system of the invention from the mixtures according to the invention manufacture. The basecoats according to the invention are Accordingly, it is the color and / or effect layers of Multicoat paint systems, which are essential to the overall visual impression (Appearance) determine.

The Inventive basecoats have surprisingly at a particularly high Kochergrenze a high pinprick limit. They are free of other paint defects like clouds, specks, pimples, craters, orange peel and cracks. she have an excellent intercoat adhesion. Because the waterborne basecoats of the invention the color and / or effect pigments (B) very good disperse, have the basecoats of the invention also at a comparatively low pigment-to-binder ratio very high opacity and excellent optical effects on top of that as well can reproduce perfectly.

ever according to intended use, the mixtures according to the invention are based on conventional and known temporary or permanent substrates applied.

Preferably be for the production of films and moldings according to the invention conventional and known temporary Substrates used, such as metal and plastic bands or hollow body Metal, glass, plastic, wood or ceramics that are easily removed can be without the films of the invention and moldings are damaged.

Become the mixtures according to the invention for the preparation used by coatings, adhesives and gaskets used permanent substrates.

• – mit Muskelkraft, Heißluft oder Wind betriebenen Fortbewegungsmittel zu Lande, zu Wasser oder zur Luft, wie Fahrräder, Draisinen, Ruderboote, Segelboote, Heißluftballons, Gasballons oder Segelflugzeuge, sowie Teilen hiervon,
• – mit Motorkraft betriebenen Fortbewegungsmittel zu Lande, zu Wasser oder zur Luft, wie Motorräder, Nutzfahrzeuge oder Kraftfahrzeuge, insbesondere PKW, Über- oder Unterwasserschiffe oder Flugzeuge, sowie Teile hiervon,
• – stationäre Schwimmkörper, wie Bojen oder Teilen von Hafenanlagen
• – Bauwerke im Innen- und Außenbereich,
• – Türen, Fenstern und Möbel und
• – Glashohlkörper,
• – industrielle Kleinteile, wie Schrauben, Mutter, Randkappen oder Felgen,
• – Behälter, wie Coils, Container oder Emballagen,
• – elektrotechnische Bauteile, wie elektronische Wickelgüter, beispielsweise Spulen,
• – optische Bauteile,
• – mechanische Bauteile und
• – weiße Ware, wie Haushaltsgeräte, Heizkessel und Radiatoren.

Preferably, the substrates are um

• - on land, at sea, or with water, hot air or wind powered means of locomotion to air, such as bicycles, trolleys, rowing boats, sailboats, hot air balloons, gas balloons or gliders, and parts thereof,
• - powered by motor means of transport by land, sea or air, such as motorcycles, commercial or motor vehicles, in particular passenger cars, surface or underwater vessels or aircraft, and parts thereof,
• - stationary floats, such as buoys or parts of docks
• - buildings inside and outside,
• - Doors, windows and furniture and
• - glass hollow body,
• - small industrial parts, such as screws, nuts, peripheral caps or rims,
• - containers, such as coils, containers or packaging,
• Electrotechnical components, such as electronic winding goods, for example coils,
• - optical components,
• - mechanical components and
• - white goods, such as household appliances, boilers and radiators.

The inventive films and moldings can also serve as substrates.

Especially the substrates are car bodies and parts hereof. The mixtures according to the invention or the coatings according to the invention produced therefrom serve preferably the original finish of the automobile bodies (OEM) or the refinish of inventive and non-inventive first coats. The first coatings according to the invention, in particular those containing a basecoat according to the invention, have excellent recoatability. The inventive refinishes adhere excellently to the novel and non-inventive primary coatings.

methodical the application of the mixtures according to the invention has no special features but can through all the usual and known, for the particular mixture suitable application methods, such. Spraying, spraying, Doctoring, brushing, pouring, Diving, trickling or rolling done. Preferably, spray application methods applied.

at The application is recommended, excluding actinic Working radiation when the mixtures of the invention in addition to curable by actinic radiation are.

• – DE 100 43 405 C1 , Spalte 2, Absatz [0009], bis Spalte 3, Absatz [0017], und Spalte 8, Absatz [0052], bis Spalte 9, Absatz [0056] Ende,
• – DE 199 14 98 A1 , Spalte 16, Zeile 54, bis Spalte 18, Zeile 54,
• – DE 199 30 067 A1 , Seite 15, Zeile 23, bis Seite 16, Zeile 36, oder
• – DE 199 40 855 A1 , Spalte 30, Zeile 39, bis Spalte 31, Zeile 48, und Spalte 32, Zeilen 15 bis 29,

bekannt sind.In particular, wet-on-wet processes and structures can be used for the production of the multicoat paint systems according to the invention, as described, for example, in German patent applications

• - DE 100 43 405 C1 , Column 2, paragraph [0009], to column 3, paragraph [0017], and column 8, paragraph [0052], to column 9, paragraph [0056] end,
• - DE 199 14 98 A1 , Column 16, line 54, to column 18, line 54,
• - DE 199 30 067 A1 , Page 15, line 23, to page 16, line 36, or
• - DE 199 40 855 A1 , Column 30, line 39, to column 31, line 48, and column 32, lines 15 to 29,

are known.

It is a very significant advantage of the use according to the invention, that basically the primer coatings, anti-corrosion coatings, Functional coatings, surfacer coatings, antistonechip primers, Basecoats and solid-color topcoats, but especially the Basecoats, the multicoat paint systems according to the invention from the mixtures according to the invention can be produced.

The hardening the mixtures according to the invention generally takes place after a certain rest period or ventilation time. It can last for 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 to 45 minutes. The rest period is for example for the course and degassing of the applied mixtures according to the invention and to the evaporation of volatile Ingredients such as any solvent. The ventilation can through an increased Temperature, which leads to a hardening is not enough, and / or by a reduced humidity be accelerated.

The thermal curing the applied mixtures of the invention takes place, for example, with the aid of a gaseous, liquid and / or solid, hot medium, like hot Air, heated oil or heated rollers, or of microwave radiation, infrared light and / or near infrared light (NIR). Preferably, the heating takes place in a convection oven or by irradiation with IR and / or NIR lamps. As during curing With actinic radiation, the thermal curing can also be gradual respectively. Advantageously, the thermal curing takes place at temperatures from room temperature to 200 ° C.

The thermal curing the mixtures according to the invention can also be under extensive or complete exclusion of oxygen carried out become.

In the context of the present invention, the oxygen is considered largely excluded if its concentration at the surface of the applied mixtures according to the invention <21 vol .-%, preferably <18 vol .-%, preferably <16 vol .-%, particularly preferably 14 vol. -%, most preferably 10 vol .-% and in particular <6 Vol .-% is.

in the In the context of the present invention, the oxygen is considered completely excluded, if its concentration at the surface is below the detection limit the usual and known detection methods.

Prefers the concentration of oxygen is ≥ 0.001% by volume, more preferably ≥ 0.01% by volume, most preferably ≥ 0.1 Vol .-% and in particular ≥ 0.5 Vol .-%.

The desired concentrations of oxygen can be achieved by the methods described in the German patent DE 101 30 972 C1 , Page 6, paragraphs [0047] to [0052], described measures or by the application of slides are set.

The curing with actinic radiation can by means of the usual and known devices and methods, as described for example in the German patent application DE 198 18 735 A1 , Column 10, lines 31 to. 61, the German patent application DE 102 02 565 A1 , Page 9, paragraph [0092], to page 10, paragraph [0106], of the German patent application DE 103 16 890 A1 , Page 17, paragraphs [0128] to [0130], in International Patent Application WO 94/11123, page 2, lines 35, to page 3, line 6, page 3, lines 10 to 15, and page 8, lines 1 to 14, or the American patent US 6,743,466 B2 , Column 6, line 53, to column 7, line 14, are performed.

The thermoset and thermoplastic, in particular thermosetting, materials, in particular the films according to the invention, Moldings, coatings, adhesive layers and seals are suitable excellent for the coating, gluing, sealing, wrapping and packaging of the above described substrates.

The resulting substrates according to the invention, coated with coatings according to the invention, bonded with adhesive layers according to the invention, with seal according to the invention sealed and / or with films and / or moldings according to the invention wrapped or packed, have excellent performance properties associated with a particularly long service life.

Example and Comparative test

Comparative test

The preparation of the water-based paint V1 and the multicoat paint system V1

Example 1 of the German patent DE 100 43 405 C1 , Column 12, line 57, to column 13, line 1, i. V. m. Column 11, line 26, to column 12, line 31, was repeated. The water-based paint V1 in question contained tributyl phosphate. The visual evaluation of the wedge-shaped basecoat V1 showed a pinhole limit of 20 μm and a cooker limit of 26 μm.

The preparation of the water-based paint 1 and the multi-layer coating 1

Of the Comparative experiment was repeated except that in place of tributyl phosphate the same amount of TBEP was used. The visual evaluation the wedge-shaped applied basecoat V1 gave a pinprick of 23 μm and a cooker limit of 43 microns. Otherwise, the multi-layer paint 1 had the same advantageous Properties such as the multi-layer coating V1 on.

The Results substantiate that TBEP is the pinprick border and in particular can significantly increase the limits of the digester without this to a deterioration of the other material application-related Properties leads.

Claims (18)

Physically, thermally or thermally and with actinic radiation curable, aqueous mixtures containing (A) at least one saturated, unsaturated and / or grafted with olefinically unsaturated compounds, ionically and / or nonionically stabilized polyurethane as a binder, (B) at least one color and or effect pigment and (C) at least one phosphoric acid ester of general formula I: (R ¹ ORO) ₃ P = O (I) wherein the variables have the following meaning: R alkanediyl group having 2 to 10 carbon atoms and R ¹ alkyl group having 2 to 10 carbon atoms. Mixtures according to Claim 1, characterized the alkanediyl group R is selected from the group consisting of ethylene, Trimethylene, tetramethylene, pentamethylene, hexamethylene, heptane-1,7-diyl, octane-1,8-diyl, Nonane-1,9-diyl and decane-1,10-diyl. Mixtures according to claim 3, characterized in that the alkanediyl group R is selected from the group consisting of ethylene, trimethylene and tetra methylene, is selected Mixtures according to Claim 4, characterized the alkanediyl group R is ethylene. Mixtures according to one of claims 1 to 4, characterized in that the alkyl group R ¹ from the group consisting of ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, is selected. Mixtures according to claim 5, characterized in that the alkyl group R ^{1 is selected} from the group consisting of ethyl, propyl, n-butyl, n-pentyl and n-hexyl. Mixtures according to claim 6, characterized in that the alkyl group R ^{1 is} n-butyl. Mixtures according to Claim 4 or 7, characterized that the phosphoric acid ester (C) tris (2-butoxyethyl) phosphate TBEP. Mixtures according to one of Claims 1 to 8, characterized that they are the phosphoric acid ester (C) in an amount of 0.1 to 5 wt .-%, based on the mixture, contain. Mixtures according to one of Claims 1 to 9, characterized that contain at least one additive (D). Mixtures according to Claim 10, characterized that the additive (D) from the group consisting of the binders (A) various binders, crosslinking agents, neutralizing agents, Catalysts for the networking, adhesion promoters, additives to improve the Substrate wetting, surface-smoothening additives, matting agents, Light stabilizers, polymerization inhibitors, corrosion inhibitors, Biocides, flame retardants, initiators for thermal crosslinking, Photoinitiators, of the pigments (B) different, fluorescent, electrically conductive and / or magnetically shielding pigments and metal powders, organic and inorganic, transparent or opaque fillers and nanoparticles, organic dyes, rheology aids, leveling agents, Wetting agents, emulsifiers, defoamers and of the phosphoric acid esters (C) various organic solvents, selected is. Process for the production of physical, thermal or thermally and actinically radiation curable, aqueous mixtures according to any one of claims 1 to 11, characterized in that at least one binder (A), at least one color and / or effect pigment (B) and at least a phosphoric acid ester (C) mixed together in the presence of water and the resulting Homogenized mixture. Method according to claim 12, characterized in that that at least one additive (D) is added. Use of physical, thermal or thermal and aqueous curable with actinic radiation Mixtures according to one the claims 1 to 11 and that produced by the method according to claim 12 or 13, physically, thermally or thermally and with actinic radiation curable, aqueous Mixtures for producing color and / or effect thermosetting or thermoplastic materials. Use according to claim 14, characterized that the color and / or effect thermoset or thermoplastic Materials coatings, adhesive layers and seals as well as molded parts and slides are. Use according to claim 15, characterized that the coating materials are used as primers, primers, fillers, basecoats, Solid-color topcoats and clearcoats for the production of single-layer or multi-layered Primer coatings, anticorrosive coatings, antistonechip primers, Surfacer coats, Functional coatings, basecoats and solid-color topcoats be used. Use according to claim 16, characterized that the basecoats of the production of single or multi-layer basecoats in the context of color and / or effect multicoat paint systems serve. Use according to claim 17, characterized that the color and / or effect multi-layer coatings with Help be prepared by wet-in-wet process.